A 1-iminobutadiene-iron tricarbonyl [Fe(CO)(3)] complex (1) reacts with various organometallic nucleophiles in a stereoselective manner, and especially, by use of organocerium reagents, only single secondary amine complexes (2) were obtained in good yields. Application of this methodology was demonstrated in the asymmetric synthesis of hydroxyethylidene dipeptide isostere from the chiral starting material N-{(2R)-(2E)-tricarbonyl[2-5-eta-2,4-pentadienylidene]iron} benzylamine (1b).